Acid Dissociation in HCl-Water Clusters is Temperature Dependent and Cannot be Detected Based on Dipole Moments.

Abstract

The dissociation of acids in aqueous environments at low temperatures in the presence of a limited amount of water is underlying a wealth of processes from atmospheric to interstellar science. For the paradigmatic case of HCl(H_{2}O)_{n} clusters, our extensive abinitio path integral simulations quantify in terms of free energy differences and barriers that n=4 water molecules are indeed required to dissociate HCl at low temperatures. Increasing the temperature, however, reverses the process and thus counteracts dissociation by fluctuation-driven recombination. The size of the electric dipole moment is shown to not correlate with the acid being in its dissociated or molecular state, thus rendering its measurement as a function of n unable to detect the dissociation transition.